CA1297227C - Process for the production of finely divided polyisocyanates containing urea groups - Google Patents
Process for the production of finely divided polyisocyanates containing urea groupsInfo
- Publication number
- CA1297227C CA1297227C CA000550868A CA550868A CA1297227C CA 1297227 C CA1297227 C CA 1297227C CA 000550868 A CA000550868 A CA 000550868A CA 550868 A CA550868 A CA 550868A CA 1297227 C CA1297227 C CA 1297227C
- Authority
- CA
- Canada
- Prior art keywords
- acid
- group
- denotes
- amino
- sulphonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
- C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
- C07C273/1827—X being H
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7825—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing ureum groups
Abstract
PROCESS FOR THE PRODUCTION OF
FINELY DIVIDED POLYISOCYANATES
CONTAINING UREA GROUPS
ABSTRACT OF DISCLOSURE
The present invention is directed to a process for the preparation of finely divided solid polyiso-cyanates containing urea groups by reacting organic polyisocyanates which are free from urea groups with water in an aqueous emulsion, characterized in that the reaction is carried out in the presence of an emulsion-and dispersion-stabilizing compound.
Le A 24 814
FINELY DIVIDED POLYISOCYANATES
CONTAINING UREA GROUPS
ABSTRACT OF DISCLOSURE
The present invention is directed to a process for the preparation of finely divided solid polyiso-cyanates containing urea groups by reacting organic polyisocyanates which are free from urea groups with water in an aqueous emulsion, characterized in that the reaction is carried out in the presence of an emulsion-and dispersion-stabilizing compound.
Le A 24 814
Description
~7Z27 Mo-2985 LeA 24,814 PROCESS FOR ~HE PRODUCTION OF
FINELY DIVIDED POLYISOCYANATES
CONTAINING UREA GROUPS
Background Of The Invention 5 Field Of The Invention This invention relates to a process for the preparation of finely divided solid polyisocyanates containing urea groups by the reaction of organopoly-isocyanates which are free from urea groups with water lO in the presence of ~ stabilizing compound containing at least one hydrophilic and at least one isocyanate reactive group and optionally in the presence of conventional emulsifiers and/or cata~ysts and/or bases.
`Description Of T e Prior Art Processes for the preparation of solid poly-isocyanates containing urea groups by the reaction of organic polyisocyanates which are free from urea groups with an exce~s of water as reactive medium are already known ~inter alia US Patent 3,906,019). Since in these 20 processes the reaction products immedLately cake together and are therefore difficult to work up and process, attemp~s have been made to prepare these reaction products in a finely divided form and in quantitative yields. Accordlng to the teaching of DOS
25 3,438,527, this object may be achieved by carrying out the reaction in the presence of a high molecular weight protective colloid such as a polyacrylate, cellulose, polyvinyl alcohol, etc. Although these high molecular weight protective colloids are highly effective, their 30 solubility in water may cause long production runs.
Moreover, the protectiv~ colloids are liable to be deposited as a film on the surface of the polyiso-cyanates containing urea groups, thereby impairing the Le A 24 814 k 72~7 reactivity of these polyisocyanates, especia]ly if they are kept in storage for some time.
It is therefore an object of the present inven-tion to provide a process for the preparation of poly-S isocyanates containing urea groups wherein the reactionproducts are no~ only obtained quantitatively in a very finely divided form but are also not impaired in their reactivity.
SUMMARY OF THE INVENTION
The present invention is directed to a process for the preparation of finely divided solid polyiso-cyanates containing urea groups by reacting organic polyisocyanates which are free from urea groups with water in an aqueous emulsion, characterized in that the reaction is carried out in the presence of an emulsion-and dispersion-stabilizing compound corresponding to the general formula (I) (X~a-R-~Y~b (I) wherein X denotes a NH2 group, a NHRl group in which Rl stands for a Cl-C10-alkyl residue, which contains optional-ly a tert. amino group, an OH-group or an SH-group.
R denotes an aromatlc group containing 6 to 20, preferably 6 to 10 carbon atoms, a heteroaromatic group containing 5 to 20, preferably 6 to 10 carbon atoms and at least one oxygen and/or nitrogen atom in the ring system, an aliphatlc group containing 2 to 20, preferably 2 to 10 carbon atoms or a cyclo-aliphatic group containing 4 to 20, preferably 4 to 10 carbon atoms, the above-mentioned groups being op~ionally substituted wi~h halogen atoms such as chlorine or bromine, Mo-2985-Ca - 2 -LeA 24,814-Ca ' ~9.
`- ~Z97~:X7 Y denotes COOH, COO M~ in which M stands for an alkali metal, an alkaline earth metal, NH4 or a NH-(R )3 group in which R2 = hydroxyalkyl, alkoxyalkyl or alkyl with 1 to 10, preferably 1 to 4 carbon atoms;
s or Y denotes S03H, S03 M~ in which M has the meaning previously indicated; or Y denotes -N(R )2 or a ~H(R2)2Z~ group in which Z~ denotes a carboxylate or sulphonate group and R has the meaning previously indica~ed; or Y denotes a group of general ormula lo (II) -(CH2-CH2- ~ CH2-CHO)y R4 (II
R
wherein R3 denotes a Cl-C6, preferably a Cl-C4-alkyl group, R4 denotes hydrogen or a Cl-C6 alkyl group 9 preferably hydrogen or a Cl-C4 alkyl group and x and y may be i.dentical or diferent and each represent an integer with a value o O to 50, preferably O to 5 and wherein the sum of x ~ y is at least 1, a and b, which may be identical or different, each represent an integer with a value rom 1 to 3, preferably 1 or ~, provided that i) when X stands for OH or SH, R must not be an aromatic or heteroaromatic group and ii) wl~en Y stands for a group of the general 2 formula (II), X may only sta~d for NH2 or NHR
and R is a chemical bond, or the reaction may be carried out in the presence of an alkali metal hydrogen sulphite, preferably sodium 0 hydrogen sulphite.
DETA LED_DESC~IPTION OF THE INVENTION
The starting polyisocyanates, which are free from urea groups and used for the process according to the invention, include aliphatic, cycloaliphatic, arali-5 phatic, aromatic or heterocyclic polyisocyanates of the Mo-2935-Ca - 3 -LeA 24,814-Ca ~LZ97ZZ7 kind described, for example 9 by W. Siefken in Justus LiPbigs Annalen der Chemie, 562, pages 75 to 136 9 for example those corresponding to the formula Q(NCO)n 5 wherein n = 2 to 4, preferably 2 and Q denotes an aliphatic hydrocarbon grsup having 2 to 18, preferably 6 to 10 carbon atoms, a cycloali-phatic hydrocarbon group hav~ng 4 to 15, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15, preferably 6 to 13 carbon atoms 9 or an araliphatic hydrocarbon group having 8 to 15, preferably 8 to 13 carbon atoms.
Examples of these polyisocyanates include ethylene diisocyanate, 1,4-te~ramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diiso-cyanate, cyclobutane-1,3-diisoeyanate, cyclohexane-1,3-and -1,4-diisocyanate and any mixtures of their stereo-20 isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl cyclohexane (DE-Auslegeschrift 1,202,785, US Patent Specification 3,401,190), 2,4- and 2,6-hexa-hydrotoluylene diisocyanate and any mixtureæ of these isomers, hexahydro-1,3- and/or -1,4-phenylene diiso-25 cyanate 9 perhydro-2,4'- and/or 4,4'-diphenylmethane diisocyanate, 1,3- and 1 9 4-phenylene diisocyanate, 2 9 4-and 2,6-toluylene diisocyanate and any mix~ures of ~hese isomers, diphenylmethane-2,4'-, _4,ll'_ and/or -2,2'-di-isocyanate and naphthylene-1,5~diisocyanate~
Additional examples include triphenylmethane-4, 4'94"-trii~ocyanate; polyphenyl-polymethylene polyiso-cyanates obtained by aniline-formaldehyde condensation followed by phosgenation such as those described in Le A 24 814 1297Z~7 GB Pat~nt Specifications 874,430 and 848,671; perchlori-nated aryl polyisocyanates a~ described, for example in DE Auslegeschrift 1,157,601 (US Patent Specification 3~277,138); ncrbornane diisocyanates according to 5 US Patent Specification 3,4~2,330; polyisocyanates containing allophanate groups as described, for example, in GB Patent Speoification 994,890, BE Patent Speci~i-cation 761,626 and NL Patent Specificat~on 7,102,524;
polyisocyanates containing isocyanurate groups as 10 described, for example, in US Patenk Specification 3,001~73, DE Patent Specifications 1,022,789, 1,222,067, and 1,027,394 and in DE-Ofenlegungsschriften 1,929,034 and 2,004,048; polyisocyanates containing urethane groups, for example~ as described in BE-Patent 15 Specification 752,261 or in US Patent Specifications 3,394,164 and 3,644,457; polyisocyanates prepared by telomerization reactions as described, for example, in US Patent Specification 3,654,106; polyi80- cyanates containing ester groups such as those mentioned, for 20 example, în GB Patent Specifications 965,474 and 1,072,956, US Paten~ Specification 3,567,763 and DE Patent Specification 1,231,688; reaction products of the above-mentioned isocyanates with acetals according to DE Patent Spccification 1,072,385; and polyiso-25 cyanates containing polymeric fatty acid estersaccording to US Patent Specification 3,4S5,883. The commercially readily available polyisocyanates are in most cases particularly preferred, e.g. 2,4- and 2,6-toluylene diisocyanate and any mixtures of these isomers 30 ("TDI"), polyphenyl-polymethylene polyisocyanates which are obtainable by aniline-formaldehyde condensation followed by phosgenation ("crude MDI") and polyiso-cyanates containing urethane groups, allophana~e groups or isocyanurate groups ("modified polyisocyanates"), 35 especially those modifie~ polyisocyanates which are derived from 2,4- and/or 2,6-toluylene diisocyanate or Le A 24 814 ~7~27 from 4,4'-9 2,4'- andlor 2,2l-diphenylmethane diiso-cyanate. Toluylene-2,4-diisocyanate is especially preferred.
The polyisocyanates may be used in the form of 5 a ~concentrated) solution in a solvent which is inert towards th~ polyisocyanates and immiscible with water.
These preferred solvents include aliphatic or aromatic hydrocarbons such as n-hexane, cyclohexane, isooctane, benzene, toluene, ~ylene or hydrophobic plasticizers.
The stabilizing, preferably low molecular weight compound, corresponding ~o the above general formula (I) is preferably a compound in which X and Y
have the following meaning:
1. X = NH2 Y = COOH, e.g., 2-, 3-, or 4~aminobenzoic acid, 4-chloranthranilic acid, 6-chloran-thranilic acid, 3-amino-4-methyl-benzoic acid, 3-aminocinnamic acid, 5-aminoisophthalic acid, 3-amino-salicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, aminoacetic acid, N-methylaminoacetic acid, 3-amino-propanoic acid, 4-amino-butanoic acîd, 6-aminohexanoic acid, L(+)-2,6-diaminohexanoic acid, ll-aminoundecanoic acid, L(+)-amino-butane diacid, L(+)-aminopentane diacid and DL-methiamine.
FINELY DIVIDED POLYISOCYANATES
CONTAINING UREA GROUPS
Background Of The Invention 5 Field Of The Invention This invention relates to a process for the preparation of finely divided solid polyisocyanates containing urea groups by the reaction of organopoly-isocyanates which are free from urea groups with water lO in the presence of ~ stabilizing compound containing at least one hydrophilic and at least one isocyanate reactive group and optionally in the presence of conventional emulsifiers and/or cata~ysts and/or bases.
`Description Of T e Prior Art Processes for the preparation of solid poly-isocyanates containing urea groups by the reaction of organic polyisocyanates which are free from urea groups with an exce~s of water as reactive medium are already known ~inter alia US Patent 3,906,019). Since in these 20 processes the reaction products immedLately cake together and are therefore difficult to work up and process, attemp~s have been made to prepare these reaction products in a finely divided form and in quantitative yields. Accordlng to the teaching of DOS
25 3,438,527, this object may be achieved by carrying out the reaction in the presence of a high molecular weight protective colloid such as a polyacrylate, cellulose, polyvinyl alcohol, etc. Although these high molecular weight protective colloids are highly effective, their 30 solubility in water may cause long production runs.
Moreover, the protectiv~ colloids are liable to be deposited as a film on the surface of the polyiso-cyanates containing urea groups, thereby impairing the Le A 24 814 k 72~7 reactivity of these polyisocyanates, especia]ly if they are kept in storage for some time.
It is therefore an object of the present inven-tion to provide a process for the preparation of poly-S isocyanates containing urea groups wherein the reactionproducts are no~ only obtained quantitatively in a very finely divided form but are also not impaired in their reactivity.
SUMMARY OF THE INVENTION
The present invention is directed to a process for the preparation of finely divided solid polyiso-cyanates containing urea groups by reacting organic polyisocyanates which are free from urea groups with water in an aqueous emulsion, characterized in that the reaction is carried out in the presence of an emulsion-and dispersion-stabilizing compound corresponding to the general formula (I) (X~a-R-~Y~b (I) wherein X denotes a NH2 group, a NHRl group in which Rl stands for a Cl-C10-alkyl residue, which contains optional-ly a tert. amino group, an OH-group or an SH-group.
R denotes an aromatlc group containing 6 to 20, preferably 6 to 10 carbon atoms, a heteroaromatic group containing 5 to 20, preferably 6 to 10 carbon atoms and at least one oxygen and/or nitrogen atom in the ring system, an aliphatlc group containing 2 to 20, preferably 2 to 10 carbon atoms or a cyclo-aliphatic group containing 4 to 20, preferably 4 to 10 carbon atoms, the above-mentioned groups being op~ionally substituted wi~h halogen atoms such as chlorine or bromine, Mo-2985-Ca - 2 -LeA 24,814-Ca ' ~9.
`- ~Z97~:X7 Y denotes COOH, COO M~ in which M stands for an alkali metal, an alkaline earth metal, NH4 or a NH-(R )3 group in which R2 = hydroxyalkyl, alkoxyalkyl or alkyl with 1 to 10, preferably 1 to 4 carbon atoms;
s or Y denotes S03H, S03 M~ in which M has the meaning previously indicated; or Y denotes -N(R )2 or a ~H(R2)2Z~ group in which Z~ denotes a carboxylate or sulphonate group and R has the meaning previously indica~ed; or Y denotes a group of general ormula lo (II) -(CH2-CH2- ~ CH2-CHO)y R4 (II
R
wherein R3 denotes a Cl-C6, preferably a Cl-C4-alkyl group, R4 denotes hydrogen or a Cl-C6 alkyl group 9 preferably hydrogen or a Cl-C4 alkyl group and x and y may be i.dentical or diferent and each represent an integer with a value o O to 50, preferably O to 5 and wherein the sum of x ~ y is at least 1, a and b, which may be identical or different, each represent an integer with a value rom 1 to 3, preferably 1 or ~, provided that i) when X stands for OH or SH, R must not be an aromatic or heteroaromatic group and ii) wl~en Y stands for a group of the general 2 formula (II), X may only sta~d for NH2 or NHR
and R is a chemical bond, or the reaction may be carried out in the presence of an alkali metal hydrogen sulphite, preferably sodium 0 hydrogen sulphite.
DETA LED_DESC~IPTION OF THE INVENTION
The starting polyisocyanates, which are free from urea groups and used for the process according to the invention, include aliphatic, cycloaliphatic, arali-5 phatic, aromatic or heterocyclic polyisocyanates of the Mo-2935-Ca - 3 -LeA 24,814-Ca ~LZ97ZZ7 kind described, for example 9 by W. Siefken in Justus LiPbigs Annalen der Chemie, 562, pages 75 to 136 9 for example those corresponding to the formula Q(NCO)n 5 wherein n = 2 to 4, preferably 2 and Q denotes an aliphatic hydrocarbon grsup having 2 to 18, preferably 6 to 10 carbon atoms, a cycloali-phatic hydrocarbon group hav~ng 4 to 15, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15, preferably 6 to 13 carbon atoms 9 or an araliphatic hydrocarbon group having 8 to 15, preferably 8 to 13 carbon atoms.
Examples of these polyisocyanates include ethylene diisocyanate, 1,4-te~ramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diiso-cyanate, cyclobutane-1,3-diisoeyanate, cyclohexane-1,3-and -1,4-diisocyanate and any mixtures of their stereo-20 isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl cyclohexane (DE-Auslegeschrift 1,202,785, US Patent Specification 3,401,190), 2,4- and 2,6-hexa-hydrotoluylene diisocyanate and any mixtureæ of these isomers, hexahydro-1,3- and/or -1,4-phenylene diiso-25 cyanate 9 perhydro-2,4'- and/or 4,4'-diphenylmethane diisocyanate, 1,3- and 1 9 4-phenylene diisocyanate, 2 9 4-and 2,6-toluylene diisocyanate and any mix~ures of ~hese isomers, diphenylmethane-2,4'-, _4,ll'_ and/or -2,2'-di-isocyanate and naphthylene-1,5~diisocyanate~
Additional examples include triphenylmethane-4, 4'94"-trii~ocyanate; polyphenyl-polymethylene polyiso-cyanates obtained by aniline-formaldehyde condensation followed by phosgenation such as those described in Le A 24 814 1297Z~7 GB Pat~nt Specifications 874,430 and 848,671; perchlori-nated aryl polyisocyanates a~ described, for example in DE Auslegeschrift 1,157,601 (US Patent Specification 3~277,138); ncrbornane diisocyanates according to 5 US Patent Specification 3,4~2,330; polyisocyanates containing allophanate groups as described, for example, in GB Patent Speoification 994,890, BE Patent Speci~i-cation 761,626 and NL Patent Specificat~on 7,102,524;
polyisocyanates containing isocyanurate groups as 10 described, for example, in US Patenk Specification 3,001~73, DE Patent Specifications 1,022,789, 1,222,067, and 1,027,394 and in DE-Ofenlegungsschriften 1,929,034 and 2,004,048; polyisocyanates containing urethane groups, for example~ as described in BE-Patent 15 Specification 752,261 or in US Patent Specifications 3,394,164 and 3,644,457; polyisocyanates prepared by telomerization reactions as described, for example, in US Patent Specification 3,654,106; polyi80- cyanates containing ester groups such as those mentioned, for 20 example, în GB Patent Specifications 965,474 and 1,072,956, US Paten~ Specification 3,567,763 and DE Patent Specification 1,231,688; reaction products of the above-mentioned isocyanates with acetals according to DE Patent Spccification 1,072,385; and polyiso-25 cyanates containing polymeric fatty acid estersaccording to US Patent Specification 3,4S5,883. The commercially readily available polyisocyanates are in most cases particularly preferred, e.g. 2,4- and 2,6-toluylene diisocyanate and any mixtures of these isomers 30 ("TDI"), polyphenyl-polymethylene polyisocyanates which are obtainable by aniline-formaldehyde condensation followed by phosgenation ("crude MDI") and polyiso-cyanates containing urethane groups, allophana~e groups or isocyanurate groups ("modified polyisocyanates"), 35 especially those modifie~ polyisocyanates which are derived from 2,4- and/or 2,6-toluylene diisocyanate or Le A 24 814 ~7~27 from 4,4'-9 2,4'- andlor 2,2l-diphenylmethane diiso-cyanate. Toluylene-2,4-diisocyanate is especially preferred.
The polyisocyanates may be used in the form of 5 a ~concentrated) solution in a solvent which is inert towards th~ polyisocyanates and immiscible with water.
These preferred solvents include aliphatic or aromatic hydrocarbons such as n-hexane, cyclohexane, isooctane, benzene, toluene, ~ylene or hydrophobic plasticizers.
The stabilizing, preferably low molecular weight compound, corresponding ~o the above general formula (I) is preferably a compound in which X and Y
have the following meaning:
1. X = NH2 Y = COOH, e.g., 2-, 3-, or 4~aminobenzoic acid, 4-chloranthranilic acid, 6-chloran-thranilic acid, 3-amino-4-methyl-benzoic acid, 3-aminocinnamic acid, 5-aminoisophthalic acid, 3-amino-salicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, aminoacetic acid, N-methylaminoacetic acid, 3-amino-propanoic acid, 4-amino-butanoic acîd, 6-aminohexanoic acid, L(+)-2,6-diaminohexanoic acid, ll-aminoundecanoic acid, L(+)-amino-butane diacid, L(+)-aminopentane diacid and DL-methiamine.
2. X - NH2 Y COO M , e.g. alkali metal and alkaline earth metal salts of the carboxylic acids mentioned under 1. above, salts of the above-mentioned carboxylic acids with Le A 24_814 ~7~:~7 tertiary amines, e.g. with trimethylamine~ triethylamine, dimethylbenzylamine, ~ris-hydroxy-ethyl~mine, tris-[(2-hydroxy-ethoxy)ethyl]-amine and triethylene diamine.
3. g = NH2 e.g. 2-, 3-, and 4-aminobQnzene sulphonic acid, 3-amino-6-chloro-benzene sulphonic acids, p-phenylene-diamine-2~sulphonic acid, 4-amino-toluene-2-sulphonic acid, 5-amino-toluene-2-sulphonic acid, 2-amino-15` toluene-4-sulphonic acid, 3-amino-benzyl sulphonic acid, 4-aminobenzyl-sulphonic acid, naphthionic acid, 2-aminoethane sulphonic acid 9 2-methylaminoethane sulphonic acid and 2-butylamlnoe~hane sulphonic acid,
4. X ~ N~2 Y ' S03 M, e.g. alkali metal and alkaline earth metal salts of the sulphonic acids mentioned under 3. above~ and salts of these sulphonic acids mentioned under 3. with the amines mentioned under 2. 7 he A 24 814 722~
5. X = -NH2, -NHR
Y = -N(R )2 1-Amino-3-(dimethylamino)propane, N~Bis(3-dimethylaminopropyl)amine, N-Methyl-N-(3-aminopropyl~-ethanol-amine, N,N-Diethyl-1,3-propandi-amine 9 Ris(3-aminopropyl)-methyl-amine, 1-~mino-2-diethylamino-ethane, 4-Amino-l-diethylamino-pentane, 4-Amino-l-dimethylamino-pentane~ l-Amino-2-dimethylamino-ethane,
Y = -N(R )2 1-Amino-3-(dimethylamino)propane, N~Bis(3-dimethylaminopropyl)amine, N-Methyl-N-(3-aminopropyl~-ethanol-amine, N,N-Diethyl-1,3-propandi-amine 9 Ris(3-aminopropyl)-methyl-amine, 1-~mino-2-diethylamino-ethane, 4-Amino-l-diethylamino-pentane, 4-Amino-l-dimethylamino-pentane~ l-Amino-2-dimethylamino-ethane,
6. X = NH2 or OH
Y = ~H.(R )2Z~
e.g. ammonium salts of amines containing at least one OH group, one primary and/or secondary amino group and at least one tertiary amino group and a quantity of carboxylic or sulphoni.c acid such that at least one NCO-reactive group per molecule is not converted into salt form, prefer-ably Mo-2985-Ca - 8 -LeA 24,814-Ca ~72~7 salts of N,N-dime~hyl-1,3-propylene diamine and one equivalent of acetic acid, propionic acid, l~ctic acid, dimethylolpropionic acid, methane sulphonic acid, bu~ane sulphonic acid or 2-hydroxy-ethanesulphonic acid; or salts of 2-(N,N-dime~hylamino)-ethanol, 2-~N,N-dimethylamino)-isopropanol or 2-(N,N-dimethylamino-ethoxy~-ethanol and carboxylio acids such as acetic aeid, propionic acid, benzoic acid or lactic acid,
Y = ~H.(R )2Z~
e.g. ammonium salts of amines containing at least one OH group, one primary and/or secondary amino group and at least one tertiary amino group and a quantity of carboxylic or sulphoni.c acid such that at least one NCO-reactive group per molecule is not converted into salt form, prefer-ably Mo-2985-Ca - 8 -LeA 24,814-Ca ~72~7 salts of N,N-dime~hyl-1,3-propylene diamine and one equivalent of acetic acid, propionic acid, l~ctic acid, dimethylolpropionic acid, methane sulphonic acid, bu~ane sulphonic acid or 2-hydroxy-ethanesulphonic acid; or salts of 2-(N,N-dime~hylamino)-ethanol, 2-~N,N-dimethylamino)-isopropanol or 2-(N,N-dimethylamino-ethoxy~-ethanol and carboxylio acids such as acetic aeid, propionic acid, benzoic acid or lactic acid,
7 . X = OH or SH
a ~
Y = COO M , e,g. salts of hydroxycarboxylic acids or mercaptocarboxylic acids such as lac~ic acid, glycollic acid, citric acid, dimethylolpropionlc acid, tartaric acid, or mercaptoacetic acid and the amines mentioned unde~ 2.; or
a ~
Y = COO M , e,g. salts of hydroxycarboxylic acids or mercaptocarboxylic acids such as lac~ic acid, glycollic acid, citric acid, dimethylolpropionlc acid, tartaric acid, or mercaptoacetic acid and the amines mentioned unde~ 2.; or
8 Sodium hydrogen sulphite.
To carry out the process according to the invention, a solution of water, the stabilizer according to the invention and the emulsifier and catalyst, if used, should first be prepared, for example by stirring 30 the components together. These components form the aqueous phase o the reaction mixture. The polyisocyanate is then introdueed into the aqueous phase ei~her all at once or continuously. Alternatively, all the components may be added together at the same time, 35 provided the emulsion or dispersion remains stable~
Le A 24 814 _ 9 _ ~2~7;~:27 The stabilizing compound is preferably used in a quantity of about 0.01 to 5~0% by weight, most preferably about 0.01 to 2Z by weight, based on the quantity of polyisocyanate. The quantity of organic 5 polyisocyanate may vary about 1 to 75% by wei~ht~
preferably about 10 to 30% by weight and most preferably 15 to 25% by weight, based on the whole reaction mixture~
The usual apparatus are used for p~paring the 10 emulsion, e.g. ultrasound disintegrators or apparatus in which the streams of substance~ are proJected at high speed from nozæles to be thrown against one another, parallel to one another or against solîd surfaces. It is particularly preferred to use an apparatus in which 15 the liquids are projected with high acceleration and shearing ~orces through grids or slots. 5uch apparatus are available commercially and known, for example, as mixing sirens. Apparatus operating on the rotor-stator principle are preferably used.
The emulsion is preferably prepared at about 10 to 50C, most preferably at about 23 to 25C. The poly-isocyanates should be present in the aqueous phase with an average droplet size of about 0.5 to 200 ~m, preEerably about 0.5 to 20 ~m.
After the emulsion has been prepared, the temperature for the reaction of the organic palyiso-cyanate with water should be maintained at about 10 to 80C~ preferably about 20 to 40C. The reaction is preferably carried out at normal pressure although it 30 may be carrled out at reduced or elevated pressure in suitable apparatus. An eIevated pressure may develop of its own accord due to the liberation of CO2 The em~lsion and the dispersion formed in the process should only be mildly agitated.
The polyisocyanates with urea groups formed in the reaction are only sparingly soluble in water and Le A 24 814 - 10 -~Z~7Z;~
therefore cease to undergo further reaction so that the remaining isocyanate groups in the polyisocyanates do not react with the water in the reaction mixture and gen~rally only onP isocyanate group per molecule of the S organic polyisocyanates put into the process is used up in the formation of a urea group. The isocyanate con-tents of the products obtained from the process according to the invention are in most cases only slightly below the calculated isocyanate conten~.
For the preparation of the emulsion, the aqueous or continuous phase may contain conventional non-ionic, anionic or cationic surface-active emulsifiers having an HLB (hydrophilic/lipophobic balanee) value in the range of about 10 to 18, 15 preferably about 13 to 16. The HLB value has been described in a publication of Atlas-Chemie, DL4300 Essen, published in the year 1968. The surface~active emulsifiers used may be compounds such as sodium propyl-naphthalene sulphonate, polyoxye~hylene sorbito-oleat~-20 laurate, ethoxylated nonyl phenols, polyethylene glycolethers of straight chained alcohols or polyethylene glycol esters of straight chained carboxylic acids. The emulsifier may be added not only to the aqueous phase (preferred) but also to the organic phase and is used in 25 quantities of about 0.01 to 3.0% by weight, based on the aqueous phase.
The reaction of the organic polyisocyanate with water may be accelerated by adding the catalysts used in polyurethane chemistry in the known, catalytically 30 active quantitie~, e.g. tertiary amines (N9N-dimethyl~
benzylamine, triethylamine~ pyridine or bis-(dimethyl-aminoethyl)-ether) or organometallic compounds (tributyl tin acetate, di-n-butyl~tin diacetate, Sn~ dioctoa~e or dibutyl tin dilaurate~. The catalyst is pre~erably 35 a~ded to the aqueous phase, but may alternati~ely ~e add~q only after the em~lsi~n has formed. The quantity of catalyst is Le A 24 814 - 11 -~297227 prefexably chosen so that the reaction is completed after about 2 to 8 hours and the heat of reaction evolved does not heat the mixture to temperatures above about 35C so that no external cooling need be applied.
The reaction between the organic polyisocyanate and water can be seen from the evolution of CO2.
Disturbances due to foaming may be prevented by chemically binding the CO2 by the addition of a base (e.g. aqueous sodium hydroxide solution) 80 that the 10 reaction is carried out at a pH '7 to 10 ~preferably 8.5 to 9.5). Alternatively or in addition, a commercial antifoamant such as tributyl phosphate may be added.
After termination of the reaction, which may be seen from the cessation of evolution of C92, the 15 suspension is suction filtered through a suitable filter and washed with water. It is then optionally again washed with a solvent which is inert towards isocyanates and may have a certain solubility in water, e.g. ethyl acetate or acetone, and it is finally dried in a drying 20 cupboard, preferably under vacuum, at a low temperature (50C) When tertiary amines are used as a catalyst, these may be completely transferred to the aqueous phase in the form of their salts by the addition of an 25 equivalent quantity of acid so that they will no longer be present in the solid polyisocyanate containing urea groups after this product has been worked up. Other, known processes may also be employed for removing the catalyst. If desired, the reaction may be termînated 30 before its completion by inactivating the catalyst.
When the process according to the invention is employed, the products are obtained in ~he orm of virtually perfect spheres with particle diameters generally in the region o about 1 to 20 ~m. The 35 particle diameter is determined microscopically by comparison with a calibrated scale placed in the path of the beam.
Le A 24 814 - 12 -37Z2~7 The finely divided polyisocyanates containing urea groups prepared according to the invention are preferably used in formulations for polyurethane one-component systems based on stabilized solid, finely 5 di~ided polyisocyanates which are covered in a shell of polyadduct and retarded in their reactivity, for example as described in DE-OS 3,230,757/EP-A 103,323; DE-OS
3,403,500/EP-A 150,790; DE-OS 3,418,430/EP-A 162,364;
~E-OS 3,419,429/EP-A 165,437; DE-OS 3,112,054/~P-P
10 62,780; and DE-OS 3,343,124/EP-A 145,999. It is particularly advantageous that these finely divided polyisocyanates can be used in these one-component systems without first being ground down.
General description of the experimental method of 15 carrying out the preparation of polyisocyanates containing urea g oups The given quantity of water (preferably demin-eralized water) was homogeneously mixed in a glass beaker of suitable slze with the given quantity of 20 stabilizer solution, the given quantity of emulsifier, if used (preferably in the form of a dilute solution), the given quan~ity of catalyst, if used, and any other additives used, at room temperature or with slight cooling (about 15C).
The weighed quantity of polyisocyanate used as starting material was then added and either at the same time or thereafter the two-phase mixture was vigorously mixed with cooling by means of a IJLTRA-TURRAX~' stirrer (Model T 45/N of IKA-Werk, Staufen im Breisgau with 30 Generator 45 G 6~ ~speed setting at 1/2 to 2/3 of full power) until a stable emulsion had formed (generally about 3 minutes). This emulsion was transferred to a reaction flask with ground glass top and stirred with a conventional blade stirrer.
If the aqueous phase was initially added w ithout catalyst, then the catalyst was added at this *Trademark Mo-2985-Ca - 13 -LeA 24,814-Ca ;, ,~
~7Z;~7 time. The evolution of ~2 which set in as ~he reaction gradually began wa~ measured with a ga meter. When evolution of CO2 ceased, the reaction mixture was optionally neutralized (e.g. 1~ HCl), and the ~uspens~on obtalned 5 wa~ then 3uction fi~tered, wa~hed with water and dried.
The yi~ld was v~rtually quantitative since both the filter cake and the filtrate were virtually free from unreacted starting isocyana~e.
The invention ~s ~urther illustrated, but i~
10 not intended to be llmited by the following examples in whi~h all par~ and percentages are by weigh~ unle~s otherwise specified.
EXAMPL~S
Example 1 a) Pr~paration of the polyi~ocyanate containing urea groups Aqueous pha e: 700 g of water 4.0 g of dispersion ~tabilizer solution prepared from 15 g of glycine, 56.2 g of tris(2-(hydroxyethoxy)-ethyl) amine, 134.4 g of water and 2.5 g of dimethyl-benzy.lamine a~ catalyst Organic phase: 150 g of 2,4-toluylene dii~ocyanate Product: average particle size range: 8-14 ~m i~ocyanate con~ent: 23,62% by weight b) Preparation of a polyurea polyurethane 100 part~ of a polyoxypropylene glycol polyether containing ~erminal aromatic amino groups and having ~n NH number of 47.5 (pr~pared according to DOS 2,948~419 by the hydroly~is of a prepolymer obtained rom 1 mol of polyoxypropylene glycol, molecular Le A 24 814 - 14 -~Z~ 7 weight 2000, and 2 mol of 2,4-toluylene diisocyanate) were vigorously mixed wl~h 19 parts of the polyisocyanate containing urea groups prepared in a), using a powerful stirrer with a toothed rim stirrer disc and the mixture was degasified in a water jet vacuum.
A The "thiekening temperature" of the mixture was then determined by the method described in DOS 3,230,757, page 49, and a sample plate measuring 20 ~ 20 x 0.3 cm wa~ produced from the mixture on a metal casting mold 15` (hardenîng of the liquid mixture in one hour a~ 150C).
B Another mixture was prepared in which 0.05 parts (to 100 parts of polye~her) of a polyoxypropylene glycol containing terminal aliphatic amino groups were added to the polyoxypropylene polyether containing terminal amino groups before the polyisocyanate containing urea groups was added.
The "thickening temperature" of this mixture was determined and a sample plate was again prepared. Table 1 shows the results obtained and the mechanical properties of the sample pla~es produced.
Le A 24 Bl4 - 15 -~2g72~
Tab A
.
5 Thickening Temperature 68 82 Mechanical properties:
Tensile strength DIN 53504 (MPa) 13.89 12.53 10 100 % modulus (DIN 53504) (MPa) 13.89 11.96 Elongation at break DIN 53504 (%) 150 200 15 Tear propagation resistance DIN 53515 (kN/m) 30.7 29.9 Shore hardness A 92 90 Elasticity ~IN 53512 (%) 44 46 ~mr _ _ . _ _ . _ . . __ Time for hardening 25 a sample 3 mm in thiclcness (min'/sec") 1'20" l'S0"
Le A 24 814 - 16 -~ Z~'7~ ~ ~
The experiments show the excellent reactivity of the polyisocyana~es prepared according to the invention (see thickening temperature in Experiments A
and B) and the (desired) low sensitivity towards the 5 aliphatic polyamines used for forming a reaction retarding polyurea outer shell.
Aqueous phase: 3500 g of water g of stabilizer solution prepared from 15 g of glycine 29.8 g of triethanolami~e and 134.4 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-tolyulene diiso-cyanate Product: Particle size range: 6-14 ~m NCO content: 24.30~ by weight Example 3 Aqueous phase: 3500 g of water g of stabilizer solution prepared from lS g of glycine, 29.8 g of triethanolamine and 134.4 g o~ water 12.5 g of dimethylbenzylamine as catalyst 30 Organic phase: 750 g of 2~4-toluylene diiso-cyanate The catalyst was neutralized by the addition of an equivalent quantity of lN-hydrochloric acid after termina~ion of the reaction (cessation of CO2 35 evolution).
Product: average particle size range: 8-14 ~m NCO content: 23.63% by weight Le A 24 814 - 17 -~Z~7Z27 Example 4 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 15 g of glycine.
29.8 g of triethanolamine and 134.4 g of water 10 g of 1,4-diazabicyclooctane as ca~alyst 10 Organic phase: 750 g of 2,4-toluylene diisocyanate Product: average particle size range: 5-14 ~m NCO content: 24,23% by weight ~.
Aqu ous phase: 3500 g of wa~er 5 g of stabilizer solution prepared from 60.97 g of a 41% aqueous solution of the sodium salt of 2-aminoethane-sulphonic acid and 118.23 g of dimethylbenzylamine as ca~alyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product: average particle size range: 5 15 ~m NCO content: 23.61% by weight Example 6 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 29.05 g of 94.3% 4-amino-benzoic acid, 29.8 g of triethanolamine and 120.4 g of water 12.5 g of -~thylbenz:yiamine as catalyst 35 Organic phase: 750 g of 2,~-toluylene diiso~yanate Product: average ~article size range: 4-13 ~m NCO content: 23.49% by weight Le A 24 814 ~ 18 -~l297~Z~
Example 7 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 26.2 g of 6-aminohexanoic acid, 29.8 g of triethanolamine and 123.2 g of water 12.5 g of dimethylbenzylamine as catalyst Organic pha~e: 750 g of 2,4-toluylene diisocyanate average particle size range: 5-15 ~m NCO content: 24.18% by weight lS Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 17.8 g of 3-aminopropanoic acid, 29.8 g of triethanolamine and 131.6 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate 5 Product: par~icle size range: 7-14 ~m NCO content: 23.48% by weight Example 9 Aqueous phase: 700 g of water 4 g of stabilizer solution prepared from 34.6 g of 4-aminobenzene sulphonic acid, 2~.8 g of triethanolamine and 114.8 g of wa~er 2.5 g of dimethylbenzylamine as ca~alyst Organic phase: 150 g o 2,4-toluylene diisocyanate Le A 24 814 - 19 ~Z97~7 Product: average particle size range: 7-14 ~m NCO content: 24.10% by weig~t Example 10 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 15 g of glycine, 22.4 g of 50% aqueous KOH
solution and 141.8 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product particle size range: 7-14 ~m NCO content: 22.99% by weight Exam~le 11 Aqueous phase: 3500 g of water 20 g of stabili~er solution being a 40% solution of Na-hydrogen sulphite in water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-~oluylene diisocyanate 25 Product: particle size range: 6-15 ~m NCO content: 24.04% by weight Example 12 Aqueous phase: 700 g of water 2.5 g of stabilizer solution prepared from 18.4 g of mercaptoacetic acid, 29.8 g of triethanolamine and 131.0 g of water Organic phase: 150 g of 2,4-toluylene diisocyana~e 1 g Qf dimethylbenzylamine as cataly~t was added loS hours : after emulsification Le A 24 814 20 -~97Z~7 Product: particle size range: 7-12 ~m NCO content: 22.70% by weight ~xample 13 Aqueous phase: 357 g of water 2 g of stabilizer solution prepared from 125 g of 80~ lactic acid, 20.2 g of triethylamine and 136.5 g of water 10 Organic phase: 75 g of 2,4-toluylene diisocyanate 1.25 g of dimethylbenzylamine as cataly~t was added 30 minutes after emulsiication.
Prod~ct: particle size range: 2-12 ~m NCO content: 21.00~ by weight `ExamE~le 1 4 Aqueous phase: 3500 g of water 20 g o stabilizer solution prepared from 20.4 g of N,N-dimethyl-1,3~diaminopropane, 12.0 g of ace~ic acid and 146 . 8 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product: particle size range: 3-12 ~m NCO content: 23.06% by weight Example 15 30 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 20.4 g of N,N-dimethyl-1,3-diaminopropane, 17.0 g of cyanoacetic acid and 141.8 g of water 12.5 g o~ dimethylbenzylamine as Le R 24 814 ~ 21 ~
~Z~7%~7 catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product: particle size range: 5-15 ~m NGO content: 23.72% by weight 5 ~
Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 20.4 g of N,N-dimethyl-1,3-diaminopropane, 22.5 g of 80~ lactic acid and 140.8 g of water 12.5 g of dimethylbenzylamine as catalyst 15 Organic phase: 750 g of 2,4-toluylene diisocyanate Product: particle size range: 5-13 ~m NCO content: 23.00Z by weight Example 17 Aqueous phase: 375 g of water 1.0 g of l~amino-8-hydroxy-3,6-dioxa-octane ~2,5 g o~ dimethylhenzylamine as catalyst Organic phase: 75 g of 2,4-toluylene diisocyanate 25 Product: particle size range: 10-18 ~m NCO content: 23.30% by weight.
Le A 24 814 - 22 -1~97~7 E~am~le 18 Aqueous phase: ~50D g of water 14 g of dithydroxyethyl)amine as stabilizer 12,5 g of dime~hylbenzylamine as catalys~
lQ Organic phase: 750 g of 2~4-toluylendiisocyanate Product: particle-size range: 8-15 ~m NCO-con~en~: 2~,~0% by weight.
Example 1~
Aqueous phase: ~500 g of water 15 . 3,4 g of Hydroxyethylamine as stabilizer 12,5 g of dimethylbenzylamine as catalys~
Organic phase: 750 g of 2,4-toluylendiisocyanate ~ Product: particle size range: ~-18 ~m NCO-con~ent: 24,0~ % by weight~
Example 20 Aqueous phase: 3500 g of water 5 g of N,N-Dimethyl-1,3-diamino-propane ~1-Amino-~-~dime~hyl-amino)propane) Organic phase: 750 g of 2,4-Toluylandiisocyanate Product: particle size range 2-lS ~m NCO-content: 23,36 % by weight.
~ Although the invention hai been dsscribed in detail in the foregoing for the purpose of illustration, it is to be undsrstood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art ~ithout departing from the spirit and scope of the invention axcept as it may be limi~ed by the claims.
Le A 24 814 - 2~ -
To carry out the process according to the invention, a solution of water, the stabilizer according to the invention and the emulsifier and catalyst, if used, should first be prepared, for example by stirring 30 the components together. These components form the aqueous phase o the reaction mixture. The polyisocyanate is then introdueed into the aqueous phase ei~her all at once or continuously. Alternatively, all the components may be added together at the same time, 35 provided the emulsion or dispersion remains stable~
Le A 24 814 _ 9 _ ~2~7;~:27 The stabilizing compound is preferably used in a quantity of about 0.01 to 5~0% by weight, most preferably about 0.01 to 2Z by weight, based on the quantity of polyisocyanate. The quantity of organic 5 polyisocyanate may vary about 1 to 75% by wei~ht~
preferably about 10 to 30% by weight and most preferably 15 to 25% by weight, based on the whole reaction mixture~
The usual apparatus are used for p~paring the 10 emulsion, e.g. ultrasound disintegrators or apparatus in which the streams of substance~ are proJected at high speed from nozæles to be thrown against one another, parallel to one another or against solîd surfaces. It is particularly preferred to use an apparatus in which 15 the liquids are projected with high acceleration and shearing ~orces through grids or slots. 5uch apparatus are available commercially and known, for example, as mixing sirens. Apparatus operating on the rotor-stator principle are preferably used.
The emulsion is preferably prepared at about 10 to 50C, most preferably at about 23 to 25C. The poly-isocyanates should be present in the aqueous phase with an average droplet size of about 0.5 to 200 ~m, preEerably about 0.5 to 20 ~m.
After the emulsion has been prepared, the temperature for the reaction of the organic palyiso-cyanate with water should be maintained at about 10 to 80C~ preferably about 20 to 40C. The reaction is preferably carried out at normal pressure although it 30 may be carrled out at reduced or elevated pressure in suitable apparatus. An eIevated pressure may develop of its own accord due to the liberation of CO2 The em~lsion and the dispersion formed in the process should only be mildly agitated.
The polyisocyanates with urea groups formed in the reaction are only sparingly soluble in water and Le A 24 814 - 10 -~Z~7Z;~
therefore cease to undergo further reaction so that the remaining isocyanate groups in the polyisocyanates do not react with the water in the reaction mixture and gen~rally only onP isocyanate group per molecule of the S organic polyisocyanates put into the process is used up in the formation of a urea group. The isocyanate con-tents of the products obtained from the process according to the invention are in most cases only slightly below the calculated isocyanate conten~.
For the preparation of the emulsion, the aqueous or continuous phase may contain conventional non-ionic, anionic or cationic surface-active emulsifiers having an HLB (hydrophilic/lipophobic balanee) value in the range of about 10 to 18, 15 preferably about 13 to 16. The HLB value has been described in a publication of Atlas-Chemie, DL4300 Essen, published in the year 1968. The surface~active emulsifiers used may be compounds such as sodium propyl-naphthalene sulphonate, polyoxye~hylene sorbito-oleat~-20 laurate, ethoxylated nonyl phenols, polyethylene glycolethers of straight chained alcohols or polyethylene glycol esters of straight chained carboxylic acids. The emulsifier may be added not only to the aqueous phase (preferred) but also to the organic phase and is used in 25 quantities of about 0.01 to 3.0% by weight, based on the aqueous phase.
The reaction of the organic polyisocyanate with water may be accelerated by adding the catalysts used in polyurethane chemistry in the known, catalytically 30 active quantitie~, e.g. tertiary amines (N9N-dimethyl~
benzylamine, triethylamine~ pyridine or bis-(dimethyl-aminoethyl)-ether) or organometallic compounds (tributyl tin acetate, di-n-butyl~tin diacetate, Sn~ dioctoa~e or dibutyl tin dilaurate~. The catalyst is pre~erably 35 a~ded to the aqueous phase, but may alternati~ely ~e add~q only after the em~lsi~n has formed. The quantity of catalyst is Le A 24 814 - 11 -~297227 prefexably chosen so that the reaction is completed after about 2 to 8 hours and the heat of reaction evolved does not heat the mixture to temperatures above about 35C so that no external cooling need be applied.
The reaction between the organic polyisocyanate and water can be seen from the evolution of CO2.
Disturbances due to foaming may be prevented by chemically binding the CO2 by the addition of a base (e.g. aqueous sodium hydroxide solution) 80 that the 10 reaction is carried out at a pH '7 to 10 ~preferably 8.5 to 9.5). Alternatively or in addition, a commercial antifoamant such as tributyl phosphate may be added.
After termination of the reaction, which may be seen from the cessation of evolution of C92, the 15 suspension is suction filtered through a suitable filter and washed with water. It is then optionally again washed with a solvent which is inert towards isocyanates and may have a certain solubility in water, e.g. ethyl acetate or acetone, and it is finally dried in a drying 20 cupboard, preferably under vacuum, at a low temperature (50C) When tertiary amines are used as a catalyst, these may be completely transferred to the aqueous phase in the form of their salts by the addition of an 25 equivalent quantity of acid so that they will no longer be present in the solid polyisocyanate containing urea groups after this product has been worked up. Other, known processes may also be employed for removing the catalyst. If desired, the reaction may be termînated 30 before its completion by inactivating the catalyst.
When the process according to the invention is employed, the products are obtained in ~he orm of virtually perfect spheres with particle diameters generally in the region o about 1 to 20 ~m. The 35 particle diameter is determined microscopically by comparison with a calibrated scale placed in the path of the beam.
Le A 24 814 - 12 -37Z2~7 The finely divided polyisocyanates containing urea groups prepared according to the invention are preferably used in formulations for polyurethane one-component systems based on stabilized solid, finely 5 di~ided polyisocyanates which are covered in a shell of polyadduct and retarded in their reactivity, for example as described in DE-OS 3,230,757/EP-A 103,323; DE-OS
3,403,500/EP-A 150,790; DE-OS 3,418,430/EP-A 162,364;
~E-OS 3,419,429/EP-A 165,437; DE-OS 3,112,054/~P-P
10 62,780; and DE-OS 3,343,124/EP-A 145,999. It is particularly advantageous that these finely divided polyisocyanates can be used in these one-component systems without first being ground down.
General description of the experimental method of 15 carrying out the preparation of polyisocyanates containing urea g oups The given quantity of water (preferably demin-eralized water) was homogeneously mixed in a glass beaker of suitable slze with the given quantity of 20 stabilizer solution, the given quantity of emulsifier, if used (preferably in the form of a dilute solution), the given quan~ity of catalyst, if used, and any other additives used, at room temperature or with slight cooling (about 15C).
The weighed quantity of polyisocyanate used as starting material was then added and either at the same time or thereafter the two-phase mixture was vigorously mixed with cooling by means of a IJLTRA-TURRAX~' stirrer (Model T 45/N of IKA-Werk, Staufen im Breisgau with 30 Generator 45 G 6~ ~speed setting at 1/2 to 2/3 of full power) until a stable emulsion had formed (generally about 3 minutes). This emulsion was transferred to a reaction flask with ground glass top and stirred with a conventional blade stirrer.
If the aqueous phase was initially added w ithout catalyst, then the catalyst was added at this *Trademark Mo-2985-Ca - 13 -LeA 24,814-Ca ;, ,~
~7Z;~7 time. The evolution of ~2 which set in as ~he reaction gradually began wa~ measured with a ga meter. When evolution of CO2 ceased, the reaction mixture was optionally neutralized (e.g. 1~ HCl), and the ~uspens~on obtalned 5 wa~ then 3uction fi~tered, wa~hed with water and dried.
The yi~ld was v~rtually quantitative since both the filter cake and the filtrate were virtually free from unreacted starting isocyana~e.
The invention ~s ~urther illustrated, but i~
10 not intended to be llmited by the following examples in whi~h all par~ and percentages are by weigh~ unle~s otherwise specified.
EXAMPL~S
Example 1 a) Pr~paration of the polyi~ocyanate containing urea groups Aqueous pha e: 700 g of water 4.0 g of dispersion ~tabilizer solution prepared from 15 g of glycine, 56.2 g of tris(2-(hydroxyethoxy)-ethyl) amine, 134.4 g of water and 2.5 g of dimethyl-benzy.lamine a~ catalyst Organic phase: 150 g of 2,4-toluylene dii~ocyanate Product: average particle size range: 8-14 ~m i~ocyanate con~ent: 23,62% by weight b) Preparation of a polyurea polyurethane 100 part~ of a polyoxypropylene glycol polyether containing ~erminal aromatic amino groups and having ~n NH number of 47.5 (pr~pared according to DOS 2,948~419 by the hydroly~is of a prepolymer obtained rom 1 mol of polyoxypropylene glycol, molecular Le A 24 814 - 14 -~Z~ 7 weight 2000, and 2 mol of 2,4-toluylene diisocyanate) were vigorously mixed wl~h 19 parts of the polyisocyanate containing urea groups prepared in a), using a powerful stirrer with a toothed rim stirrer disc and the mixture was degasified in a water jet vacuum.
A The "thiekening temperature" of the mixture was then determined by the method described in DOS 3,230,757, page 49, and a sample plate measuring 20 ~ 20 x 0.3 cm wa~ produced from the mixture on a metal casting mold 15` (hardenîng of the liquid mixture in one hour a~ 150C).
B Another mixture was prepared in which 0.05 parts (to 100 parts of polye~her) of a polyoxypropylene glycol containing terminal aliphatic amino groups were added to the polyoxypropylene polyether containing terminal amino groups before the polyisocyanate containing urea groups was added.
The "thickening temperature" of this mixture was determined and a sample plate was again prepared. Table 1 shows the results obtained and the mechanical properties of the sample pla~es produced.
Le A 24 Bl4 - 15 -~2g72~
Tab A
.
5 Thickening Temperature 68 82 Mechanical properties:
Tensile strength DIN 53504 (MPa) 13.89 12.53 10 100 % modulus (DIN 53504) (MPa) 13.89 11.96 Elongation at break DIN 53504 (%) 150 200 15 Tear propagation resistance DIN 53515 (kN/m) 30.7 29.9 Shore hardness A 92 90 Elasticity ~IN 53512 (%) 44 46 ~mr _ _ . _ _ . _ . . __ Time for hardening 25 a sample 3 mm in thiclcness (min'/sec") 1'20" l'S0"
Le A 24 814 - 16 -~ Z~'7~ ~ ~
The experiments show the excellent reactivity of the polyisocyana~es prepared according to the invention (see thickening temperature in Experiments A
and B) and the (desired) low sensitivity towards the 5 aliphatic polyamines used for forming a reaction retarding polyurea outer shell.
Aqueous phase: 3500 g of water g of stabilizer solution prepared from 15 g of glycine 29.8 g of triethanolami~e and 134.4 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-tolyulene diiso-cyanate Product: Particle size range: 6-14 ~m NCO content: 24.30~ by weight Example 3 Aqueous phase: 3500 g of water g of stabilizer solution prepared from lS g of glycine, 29.8 g of triethanolamine and 134.4 g o~ water 12.5 g of dimethylbenzylamine as catalyst 30 Organic phase: 750 g of 2~4-toluylene diiso-cyanate The catalyst was neutralized by the addition of an equivalent quantity of lN-hydrochloric acid after termina~ion of the reaction (cessation of CO2 35 evolution).
Product: average particle size range: 8-14 ~m NCO content: 23.63% by weight Le A 24 814 - 17 -~Z~7Z27 Example 4 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 15 g of glycine.
29.8 g of triethanolamine and 134.4 g of water 10 g of 1,4-diazabicyclooctane as ca~alyst 10 Organic phase: 750 g of 2,4-toluylene diisocyanate Product: average particle size range: 5-14 ~m NCO content: 24,23% by weight ~.
Aqu ous phase: 3500 g of wa~er 5 g of stabilizer solution prepared from 60.97 g of a 41% aqueous solution of the sodium salt of 2-aminoethane-sulphonic acid and 118.23 g of dimethylbenzylamine as ca~alyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product: average particle size range: 5 15 ~m NCO content: 23.61% by weight Example 6 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 29.05 g of 94.3% 4-amino-benzoic acid, 29.8 g of triethanolamine and 120.4 g of water 12.5 g of -~thylbenz:yiamine as catalyst 35 Organic phase: 750 g of 2,~-toluylene diiso~yanate Product: average ~article size range: 4-13 ~m NCO content: 23.49% by weight Le A 24 814 ~ 18 -~l297~Z~
Example 7 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 26.2 g of 6-aminohexanoic acid, 29.8 g of triethanolamine and 123.2 g of water 12.5 g of dimethylbenzylamine as catalyst Organic pha~e: 750 g of 2,4-toluylene diisocyanate average particle size range: 5-15 ~m NCO content: 24.18% by weight lS Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 17.8 g of 3-aminopropanoic acid, 29.8 g of triethanolamine and 131.6 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate 5 Product: par~icle size range: 7-14 ~m NCO content: 23.48% by weight Example 9 Aqueous phase: 700 g of water 4 g of stabilizer solution prepared from 34.6 g of 4-aminobenzene sulphonic acid, 2~.8 g of triethanolamine and 114.8 g of wa~er 2.5 g of dimethylbenzylamine as ca~alyst Organic phase: 150 g o 2,4-toluylene diisocyanate Le A 24 814 - 19 ~Z97~7 Product: average particle size range: 7-14 ~m NCO content: 24.10% by weig~t Example 10 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 15 g of glycine, 22.4 g of 50% aqueous KOH
solution and 141.8 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product particle size range: 7-14 ~m NCO content: 22.99% by weight Exam~le 11 Aqueous phase: 3500 g of water 20 g of stabili~er solution being a 40% solution of Na-hydrogen sulphite in water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-~oluylene diisocyanate 25 Product: particle size range: 6-15 ~m NCO content: 24.04% by weight Example 12 Aqueous phase: 700 g of water 2.5 g of stabilizer solution prepared from 18.4 g of mercaptoacetic acid, 29.8 g of triethanolamine and 131.0 g of water Organic phase: 150 g of 2,4-toluylene diisocyana~e 1 g Qf dimethylbenzylamine as cataly~t was added loS hours : after emulsification Le A 24 814 20 -~97Z~7 Product: particle size range: 7-12 ~m NCO content: 22.70% by weight ~xample 13 Aqueous phase: 357 g of water 2 g of stabilizer solution prepared from 125 g of 80~ lactic acid, 20.2 g of triethylamine and 136.5 g of water 10 Organic phase: 75 g of 2,4-toluylene diisocyanate 1.25 g of dimethylbenzylamine as cataly~t was added 30 minutes after emulsiication.
Prod~ct: particle size range: 2-12 ~m NCO content: 21.00~ by weight `ExamE~le 1 4 Aqueous phase: 3500 g of water 20 g o stabilizer solution prepared from 20.4 g of N,N-dimethyl-1,3~diaminopropane, 12.0 g of ace~ic acid and 146 . 8 g of water 12.5 g of dimethylbenzylamine as catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product: particle size range: 3-12 ~m NCO content: 23.06% by weight Example 15 30 Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 20.4 g of N,N-dimethyl-1,3-diaminopropane, 17.0 g of cyanoacetic acid and 141.8 g of water 12.5 g o~ dimethylbenzylamine as Le R 24 814 ~ 21 ~
~Z~7%~7 catalyst Organic phase: 750 g of 2,4-toluylene diisocyanate Product: particle size range: 5-15 ~m NGO content: 23.72% by weight 5 ~
Aqueous phase: 3500 g of water 20 g of stabilizer solution prepared from 20.4 g of N,N-dimethyl-1,3-diaminopropane, 22.5 g of 80~ lactic acid and 140.8 g of water 12.5 g of dimethylbenzylamine as catalyst 15 Organic phase: 750 g of 2,4-toluylene diisocyanate Product: particle size range: 5-13 ~m NCO content: 23.00Z by weight Example 17 Aqueous phase: 375 g of water 1.0 g of l~amino-8-hydroxy-3,6-dioxa-octane ~2,5 g o~ dimethylhenzylamine as catalyst Organic phase: 75 g of 2,4-toluylene diisocyanate 25 Product: particle size range: 10-18 ~m NCO content: 23.30% by weight.
Le A 24 814 - 22 -1~97~7 E~am~le 18 Aqueous phase: ~50D g of water 14 g of dithydroxyethyl)amine as stabilizer 12,5 g of dime~hylbenzylamine as catalys~
lQ Organic phase: 750 g of 2~4-toluylendiisocyanate Product: particle-size range: 8-15 ~m NCO-con~en~: 2~,~0% by weight.
Example 1~
Aqueous phase: ~500 g of water 15 . 3,4 g of Hydroxyethylamine as stabilizer 12,5 g of dimethylbenzylamine as catalys~
Organic phase: 750 g of 2,4-toluylendiisocyanate ~ Product: particle size range: ~-18 ~m NCO-con~ent: 24,0~ % by weight~
Example 20 Aqueous phase: 3500 g of water 5 g of N,N-Dimethyl-1,3-diamino-propane ~1-Amino-~-~dime~hyl-amino)propane) Organic phase: 750 g of 2,4-Toluylandiisocyanate Product: particle size range 2-lS ~m NCO-content: 23,36 % by weight.
~ Although the invention hai been dsscribed in detail in the foregoing for the purpose of illustration, it is to be undsrstood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art ~ithout departing from the spirit and scope of the invention axcept as it may be limi~ed by the claims.
Le A 24 814 - 2~ -
Claims (22)
1. A process for the preparation of finely divided, silid polyisocyanates containing urea groups which comprises reacting water with an organic polyisocyanate which is free from urea groups in an aqueous emulsion, which further comprises conducting the reaction in the presence of an emulsion- and dispersion-stabilizing compound corresponding to the formula (I) (X)a-R-(Y)b (I) wherein X denotes an NH2 group, an OH-group, an SH-group or a NHR1 group in which R1 represents a C1- to C10-alkyl group which may be substituted or unsubstituted with a tert. amino group, R denotes an aromatic group with 6 to 20 carbon atoms, a heteroaromatic group with 5 to 20 carbon atoms and at least one oxygen and/or nitrogen atom in the ring system, an aliphatic group with 2 to 20 carbon atoms or a cycloaliphatic group with 4 to 20 carbon atoms, said groups being substituted or unsubstituted with halogen atoms, Y denotes COOH, or COO-M+ in which M stands for an alkali metal, an alkaline earth metal, NH4 or the group NH-(R2)3 in which R2 represents hydroxyalkyl, alkoxyalkyl or alkyl with 1 to 10 carbon atoms; or Y denotes SO3H or SO3-M+ in which M is as defined above as indicated; or Y denotes -N(R2)2 or -?>H(R2)2? in which Z is a carboxylate group or a sulphonate group Mo-2985-Ca -24-and R2 is as defined above; or Y denotes a group corre-sponding to the formula (II) (II) wherein R3 denotes a C1-C6-alkyl group, R4 denotes hydrogen or a C1-C6-alkyl group and x and y, which may be identical or different, each represents an integer with a value of 0 to 50 (sum of x + y is at least 1) and a and b, which may be identical or different each repre-sent an integer with a value of 1 to 3, provided that (i) when X denotes OH or SH, then R is neither an aromatic nor a heteroaromatic group, and (ii) when Y is a group of the general formula (II), then X may only denote NH2 or NHR2 and R must stand for a chemical bond, or the reaction is carried out in the presence of an alkali metal hydrogen sulphite.
2. The process of Claim 1 wherein the stabil-izing compound used is a compound corresponding to the general formula (I) in which X denotes NH2 and Y denotes COOH, COO?M?, SO3H
or SO3?M?, or X denotes NH2 or OH and Y denotes - ?N(R2)2 Z? or X denotes OH or SH and Y denotes COO?M?.
or SO3?M?, or X denotes NH2 or OH and Y denotes - ?N(R2)2 Z? or X denotes OH or SH and Y denotes COO?M?.
3. The process of Claim 1 wherein said stabil-izing compound comprises Mo-2985-Ca LeA 24,814-Ca a) a carboxylic acid selected from the group consisting of 2-, 3- and 4-aminobenzoic acid, 4-chloranthranilic acid, 6-chloran-thranilic acid, 3-amino-4-methylbenzoic acid, 3-aminocinnamic acid, 5-aminoiso-phthalic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, aminoacetic acid, N-methylaminoacetic acid, 3-aminopropionic acid, 4-amino-butanoic acid, 6-aminohexanoic acid, L(+)-2,6-diaminohexanoic acid, 11-amino-undecanoic acid, L(+)-aminobutane diacid, L(+)-aminopentane diacid and DL-methiamine, b) an alkali metal and alkaline earth metal salt of said carboxylic acid, c) a salt of said carboxylic acid with a tertiary amine, d) a sulfonic acid selected from the group conslsting of 2-, 3-, and 4-aminobenzene sulphonic acid, 3-amino-6-chlorobenzene sulphonic acid, p-phenylenediamine-2-sulphonic acid, 4-aminotoluene-2-sulphonic acid, 5-aminotoluene-2-sulphonic acid, 2-aminotoluene-4-sulphonic acid, 3-amino-benzyl sulphonic acid, 4-aminobenzyl sulphonic acid, napthionic acid, 2-amino-ethane sulphonic acid, 2-methyl-aminoethane sulphonic acid, and 2-butyl-aminoethane sulphonic acid, e) an alkali metal and alkaline earth metal salt of said sulphonic acid, f) a salt of said sulphonic acid with a tertiary amine, Mo-2985-Ca - 26 -LeA 24,814-Ca g) an ammonium salt of an amine containing at least one OH group, primary amino group and/or secondary amino group and at least one tertiary amino group and a quantity of carboxylic or sulphonic acid such that at least one NCO-reactive group per molecule remains h) a salt of a hydroxycarboxylic acid or a mercaptocarboxylic acid, and a tertiary amine, or i) sodium hydrogen sulphite.
4. The process of Claim 3 wherein said tertiary amine comprises a member selected from the group consisting of trimethylamine, triethylamine, dimethylbenzylamine, tris-hydroxyethylamine, tris-[(2-hydroxyethoxy)ethyl]-amine and triethylene-diamine.
5. The process of Claim 1 wherein said stabil-izing compound comprises a salt of 2-(N,N-dimethylamino)-ethanol, 2-(N,N-dimethylamino)-isopropanol, or 2-(N,N-dimethylaminoethoxy)-ethanol and acetic acid, propionic acid, benzoic acid, or lactic acid.
6 The process of Claim 1 wherein said stabil-izing compound comprises a salt of a hydroxy-carboxylic acid or mercaptocarboxylic acid which comprises a member selected from the group consisting of lactic acid, glycollic acid, citric acid, dimethylol-propionic acid, tartaric acid and mercaptoacetic acid and a tertiary amine which comprises a member selected from the group consisting of trimethylamine, triethyl-amine, dimethylbenzylamine, tris-hydroxyethylamine, tris-[(2-hydroxyethoxy)ethyl]-amine and triethylene-diamine.
Mo-2985-Ca - 27 -LeA 24,814-Ca
Mo-2985-Ca - 27 -LeA 24,814-Ca
7. The process of Claim 1 wherein said stabilizing compound comprises a salt of N,N-dimethyl-1,3-propylene diamine and one equivalent of acetic acid, propionic acid, lactic acid, dimethylolpropionic acid, methane sulfonic acid, butane sulfonic acid or 2-hydroxy-ethane sulfonic acid.
8. The process of Claim 1 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight, based on the polyisocyanate which is free from urea groups.
9. The process of Claim 2 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight, based on the polyisocyanate which is free from urea groups.
10. The process of Claim 3 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight, based on the polyisocyanate which is free from urea groups.
11. The process of Claim 4 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight, based on the polyisocyanate which is free from urea groups.
12. A process for the preparation of finely divided, solid polyisocyanates containing urea groups which comprises reacting water with an organic polyisocyanate which is free from urea groups in an aqueous emulsion which further comprises conducting the reaction in the presence of an emulsion- and dispersion-stabilizing compound corresponding to the formula (I) (X)a-R-(Y)b (I) Mo-2985-Ca -28-wherein X denotes an NH2 group, an OH-group, an SH-group or a NHR1 group in which R1 represents a C1- to C10-alkyl group R denotes an aromatic group with 6 to 20 carbon atoms, a heteroaromatic group with 5 to 20 carbon atoms and at least one oxygen and/or nitrogen atom in the ring system, an aliphatic group with 2 to 20 carbon atoms or a cycloaliphatic group with 4 to 20 carbon atoms, said groups being substituted or unsubstituted with halogen atoms, Y denotes COOH, or COO-M+ in which M stands for an alkali metal, an alkaline earth metal, NH4 or the group NH-(R2)3 in which R2 represents hydroxyalkyl, alkoxyalkyl or alkyl with 1 to 10 carbon atoms; or Y denotes SO3H or SO3-M+ in which M is as defined above as indicated; or Y denotes -?H(R2)2Z? in which Z is a carboxylate group or a sulphonate group and R2 is as defined above; or Y
denotes a group corresponding to the formula (II) -CH2-CH2-O?(CH2 CHO)y-R4 (II) R3 denotes a C1-C6-alkyl group, R4 denotes hydrogen or a C1-C6-alkyl group and x and y, which may be identical or different, each represents an integer with a value of 0 to 50 and a and b, which may be identical or different each represent an integer with a value of 1 to 3, provided that (i) when X denotes OH or SH, then R is neither an aromatic or heteroaromatic group, and Mo-2985-Ca -29-(ii) when Y is a group of the general formula (II), then X may only denote NH2 or NHR2 and R must stand for a chemical bond, or the reaction is carried out in the presence of an alkali metal hydrogen sulphite.
denotes a group corresponding to the formula (II) -CH2-CH2-O?(CH2 CHO)y-R4 (II) R3 denotes a C1-C6-alkyl group, R4 denotes hydrogen or a C1-C6-alkyl group and x and y, which may be identical or different, each represents an integer with a value of 0 to 50 and a and b, which may be identical or different each represent an integer with a value of 1 to 3, provided that (i) when X denotes OH or SH, then R is neither an aromatic or heteroaromatic group, and Mo-2985-Ca -29-(ii) when Y is a group of the general formula (II), then X may only denote NH2 or NHR2 and R must stand for a chemical bond, or the reaction is carried out in the presence of an alkali metal hydrogen sulphite.
13. The process of Claim 12 wherein the stabil-izing compound use.d is a compound corresponding to the general formula (I) in which X denotes NH2 and Y denotes COOH, COO?M?, SO3H or SO3?M?, or X denotes NH2 or OH and Y denotes -?H(R2)2 Z? or X denotes OH or SH and Y denotes COO?M?.
14. The process of Claim 12 wherein said stabilizing compound comprises a) a carboxylic acid selected from the group consisting of 2-, 3- and 4-aminobenzoic acid, 4-chloranthranilîc acid, 6-chlor-anthranilic acid, 3-amino-4-methylbenzoic acid, 3-aminocinnamic acid, 5-aminoiso-phthalic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, aminoacetic acid, N-methylaminoacetic acid, 3-aminopropionic acid, 4-aminobuta-noic acid, 6-aminohexanoic acid, L(+)-2,6-diaminohexanoic acid, 11-aminoundecanoic acid, L(+)-aminobutane diacid, L(+)-amino-pentane diacid and DL-methiamine, b) an alkali metal and alkaline earth metal salt of said carboxylic acid, c) a salt of said carboxylic acid with a tertiary amine, Mo-2985-Ca - 30 -LeA 24,814-Ca d) a sulfonic acid selected from the group consisting of 2-, 3-, and 4-aminobenzene sulphonic acid, 3-amino-6-chlorobenzene sulphonic acid, p-phenylenediamine-2-sulphonic acid, 4-aminotoluene-2-sulphonic acid, 5-aminotoluene-2-sulphonic acid, 2-aminotoluene-4-sulphonic acid, 3-amino-benzyl sulphonic acid, 4-aminobenzyl sulphonic acid, napthionic acid, 2-amino-ethane sulphonic acid, 2-methylaminoethane sulphonic acid, and 2-butylaminoethane sulphonic acid, e) an alkali metal and alkaline earth metal salt of said sulphonic acid, f) a salt of said sulphonic acid with a tertiary amine, g) an ammonium salt of an amine containing at least one OH group, primary amino group and/or secondary amino group and at least one tertiary amino group and a quantity of carboxylic or sulphonic acid such that at least one primary and/or secondary amino group per molecule is not converted into the salt form, h) a salt of a hydroxycarboxylic acid or a mercaptocarboxylic acid, and a tertiary amine, or i) sodium hydrogen sulphite.
The process of Claim 14 wherein said tertiary amine comprises a member selected from the group consisting of trimethylamine, triethylamine, dimethylbenzylamine, tris-hydroxyethylamine, tris-[(2-hydroxyethoxy)ethyl]-amine and triethylene-diamine.
Mo 2985-Ca - 31 -LeA 24,814-Ca
Mo 2985-Ca - 31 -LeA 24,814-Ca
16. The process of Claim 12 wherein said stabilizing compound comprises a salt of 2-(N,N-dimethylamino)-ethanol, 2-(N,N-dimethylamino)-isopropanol, or 2-(N,N-dimethylaminoethoxy)-ethanol and acetic acid, propionic acid, benzoic acid, or lactic acid.
17. The process of Claim 12 wherein said stabilizing compound comprises a salt of a hydroxy-carboxylic acid or mercaptocarboxylic acid which comprises a member selected from the group consisting of lactic acid, glycollic acid, citric acid, dimethylol-propionic acid, tartaric acid and mercaptoacetic acid and a tertiary amine which comprises a member selected from the group consisting of trimethylamine, triethyl-amine, dimethylbenzylamine, tris-hydroxyethylamine, tris-[(2-hydroxyethoxy)-ethyl]-amine and triethylene-diamine.
18. The process of Claim 12 wherein said stabilizing compound comprises a salt of N,N-dimethyl-1,3-propylene diamine and one equivalent of acetic acid, propionic acid, lactic acid, dimethylolpropionic acid, methane sulfonic acid, butane sulfonic acid or 2-hydroxy-ethane sulfonic acid.
19. The process of Claim 12 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight based on the polyisocyanate which is free from urea groups.
20. The process of Claim 13 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight based on the polyisocyanate which is free from urea groups.
21. The process of Claim 14 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight, based on thç polyisocyanate which is free from urea groups.
Mo-2985-Ca - 32 -LeA 24,814-Ca
Mo-2985-Ca - 32 -LeA 24,814-Ca
22. The process of Claim 15 wherein said stabilizing compound is used in a quantity of about 0.01 to 5% by weight, based on the polyisocyanate which is free form urea groups.
Mo-2985-Ca - 33 -LeA 24,814-Ca
Mo-2985-Ca - 33 -LeA 24,814-Ca
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863638148 DE3638148A1 (en) | 1986-11-08 | 1986-11-08 | METHOD FOR PRODUCING POLYISOCYANATES CONTAINING FINE-PIECE UREA GROUPS |
| DEP3638148.9 | 1986-11-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1297227C true CA1297227C (en) | 1992-03-10 |
Family
ID=6313503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000550868A Expired - Lifetime CA1297227C (en) | 1986-11-08 | 1987-11-03 | Process for the production of finely divided polyisocyanates containing urea groups |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4757105A (en) |
| EP (1) | EP0270804B1 (en) |
| JP (1) | JPS63139907A (en) |
| CA (1) | CA1297227C (en) |
| DE (2) | DE3638148A1 (en) |
| ES (1) | ES2017986B3 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212230A (en) * | 1991-03-28 | 1993-05-18 | Miles Inc. | Aqueous polyurea dispersions prepared by an emulsion polymerization process |
| US5191012A (en) * | 1991-03-28 | 1993-03-02 | Miles Inc. | Aqueous dispersions of encapsulated polyisocyanates |
| DE4113416A1 (en) * | 1991-04-25 | 1992-10-29 | Bayer Ag | POLYISOCYANATE SUSPENSIONS IN RESPONDING COMPOUNDS TO ISOCYANATE GROUPS AND THEIR USE |
| US5358997A (en) * | 1992-05-07 | 1994-10-25 | Miles Inc. | Reactive aqueous polyurea dispersions prepared by an emulsion polymerization process |
| DE19835703C1 (en) * | 1998-08-07 | 1999-05-20 | Bayer Ag | N,N'-disubstituted N-(2-hydroxyalkyl)urea |
| DE10002854A1 (en) * | 2000-01-24 | 2001-07-26 | Bayer Ag | Production of finely-divided solid polyisocyanate with urea groups, used for production of polyurethane, involves reacting urea group-free polyisocyanate with water in presence of finely-divided inorganic solid |
| US20050058838A1 (en) * | 2003-09-12 | 2005-03-17 | Markusch Peter H. | Geotextile/polyurethane/composite liners based on one-component heterogeneous liquid polyurethane compositions |
| UA107670C2 (en) * | 2009-08-07 | 2015-02-10 | Dow Agrosciences Llc | Meso-sized capsules useful for the delivery of agricultural chemicals |
| CN104603171B (en) * | 2012-06-29 | 2017-05-31 | 东曹株式会社 | Carbon monoxide-olefin polymeric and the manufacture method using its polyurethane resin for manufacturing polyurethane resin |
| WO2016061068A1 (en) | 2014-10-13 | 2016-04-21 | Air Products And Chemicals, Inc. | Polyurethane catalysts from sulfur based salts |
| JP7209468B2 (en) * | 2018-02-28 | 2023-01-20 | 東ソー株式会社 | Self-emulsifying polyisocyanate composition |
| JP7334029B2 (en) * | 2018-08-23 | 2023-08-28 | 東ソー株式会社 | Self-emulsifying polyisocyanate composition and coating composition using the same |
| WO2019167958A1 (en) * | 2018-02-28 | 2019-09-06 | 東ソー株式会社 | Hydrophilizing agent for production of self-emulsifying polyisocyanate composition, self-emulsifying polyisocyanate composition, coating material composition, and coating film |
| WO2020241479A1 (en) * | 2019-05-29 | 2020-12-03 | 東ソー株式会社 | Self-emulsifying polyisocyanate composition, two-pack type coating composition and coating film |
| KR20220035422A (en) * | 2019-07-15 | 2022-03-22 | 케메탈 게엠베하 | Compositions and methods for metal pretreatment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3906019A (en) * | 1974-04-25 | 1975-09-16 | Gen Motors Corp | Preparation of di(isocyanato-tolyl) urea |
| DE2831674A1 (en) * | 1978-07-19 | 1980-02-07 | Basf Ag | AQUEOUS ISOCYANATE EMULSIONS FOR THE GLUING OF CHIPBOARDS |
| DE3438527A1 (en) * | 1984-10-20 | 1986-04-24 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYISOCYANATES CONTAINING UREA GROUPS |
-
1986
- 1986-11-08 DE DE19863638148 patent/DE3638148A1/en not_active Withdrawn
-
1987
- 1987-10-27 EP EP87115753A patent/EP0270804B1/en not_active Expired - Lifetime
- 1987-10-27 ES ES87115753T patent/ES2017986B3/en not_active Expired - Lifetime
- 1987-10-27 DE DE8787115753T patent/DE3765228D1/en not_active Expired - Lifetime
- 1987-11-03 CA CA000550868A patent/CA1297227C/en not_active Expired - Lifetime
- 1987-11-03 US US07/116,108 patent/US4757105A/en not_active Expired - Lifetime
- 1987-11-06 JP JP62279477A patent/JPS63139907A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0270804B1 (en) | 1990-09-26 |
| DE3765228D1 (en) | 1990-10-31 |
| US4757105A (en) | 1988-07-12 |
| ES2017986B3 (en) | 1991-03-16 |
| EP0270804A1 (en) | 1988-06-15 |
| DE3638148A1 (en) | 1988-05-11 |
| JPS63139907A (en) | 1988-06-11 |
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